The interaction of a Au(I) catalyst (JohnPhosAu(I)-MeCN/SbF6) and the Togni’s reagent 1, as a source of electrophilic trifluoromethyl group, has been studied in order to develop gold-catalysed alkyne trifluoromethylation reactions. Alkyne-CF3 products were prepared in moderate yields (up to 46%) by electrophilic trifluoromethylation of terminal arylalkynes with Togni’s reagent 1 in the presence of sub-stoichiometric amounts of gold catalyst (25%). The proposed addition-elimination reaction mechanism proceeds through a Au-Togni Reagent complex with a linear Togni Reagent-O-Au(I)-P-(phosphane) coordination mode (X-ray analysis). Alkyne deprotonation gives rapid formation of protonated Togni Reagent and a σ,π-acetylide dual-Au complex, confirmed by X-ray analysis. It was shown that the σ,π-dual-Au complex activates for trifluoromethylation, most likely by transfer of a [LAu]+ fragment to the alkyne substrate. The resulting reactive π-Au+-alkyne intermediate probably undergoes O-/CF3-addition of Togni Reagent, and final elimination of Togni alcohol gives the alkyne-CF3 product.